Investigation on a new electrospun gel polymer electrolyte consisting of thermoplastic polyurethane (TPU) and poly(vinylidene fluoride) (PVdF) has been made. Its characteristics were investigated by scanning electron microscopy, FT-IR, Differential Scanning Calorimeter (DSC) analysis. This kind of gel polymer electrolyte had a high ionic conductivity about 3.2 x 10(-3) S cm(-1) at room temperature, and exhibited a high electrochemical stability up to 5.0 V versus Li(+)/Li, good mechanical strength and stability to allow safe operation in rechargeable lithium-ion polymer batteries. A Li/GPE/LiFePO(4) cell delivered a high discharge capacity when it was evaluated at 0.1 degrees C rate at 25 degrees C (167.8 mAh g(-1)). And a very stable cycle performance also existed under this low current density. (C) 2011 Elsevier B.V. All rights reserved.